2000 Fiscal Year Annual Research Report

分子キラリティー認識の新規円二色性法の開発と応用

Research Project

Project/Area Number	10208202
Research Institution	Tohoku University
Principal Investigator	原田宣之東北大学, 反応化学研究所, 教授 (30006324)
Co-Investigator(Kenkyū-buntansha)	宮野壮太郎東北大学, 大学院・工学研究所, 教授 (60005501)
Keywords	円二色性スペクトル / CD励起子法 / 絶対立体化学 / 分子機械 / 光動力キラル分子モーター / チアカリックスアレーン / 光学活性スルホキシド / 分子不斉
Research Abstract	1.CD励起子法の新しい展開:単一官能基をもつ系への応用戦略我々は単一官能基をもつ系の絶対配置決定の新規方法を開発できた。(1)種々のモノアルコールに対して適用した。CD補助基をもつエステルは225nm付近に非常に強い励起子分裂型Cotton効果を示した。これはキラル部分から発色団への不斉の伝播を示す。(2)立体配座解析をCONFLEX/MM3法で行った。計算最安定配座の励起子間のねじれは正であり、実測のCDと一致した。以上、キラルモノアルコールの絶対配置を決定する新しい方法を確立できた。また本方法はキラルモノアミン化合物にも適用できた。 2.分子機械「光動力キラル分子モーター」「分子機械」とは1個の分子で出来た機械装置であり、外部エネルギーを機械的動作に変換する。我々は分子機械の1つである「光動力キラル分子モーター」の構築に世界で初めて成功した。今回、オレフィン系二重結合のシス-トランス光異性化の中間体を単離しCDを測定できた。今後、反応の熱力学を解明する。 3.キラルチアカリックスアレーンの化学カリックスアレーンによる不斉分子構築の戦略は、(1)キラル官能基の導入、(2)アキラル官能基の複数個導入に限られる。我々はチアカリックスアレーン(TCA)の架橋硫黄の酸化を利用する独自の戦略(3),(4)を確立した。まずTCAの隣接位の架橋硫黄2個を酸化し、(3)S=O中心の不斉発現を実現した。また立体配座を1,3-alternateに固定したTCAの架橋硫黄を1個酸化し、(4)骨格全体の不斉化を実現した。一方、TCAの架橋硫黄酸化体にキレーション制御型芳香族求核置換反応を適用し、反応性が基質の立体配置に依存することを明らかにした。さらにアニリンを構成単位とするCA類縁体を初めて合成した。

Research Products

(20 results)

All Other

All Publications (20 results)

[Publications] S.Kuwahara,N.Harada: "Enantioresolution and Absolute Stereochemistry of o-Substituted Diphenylmethanols."Enantiomer. 5. 109-114 (2000)
[Publications] N.Koumura,N.Harada: "Synthesis, Circular Dichroism, and Absolute Stereochemistry of 1,1'2,2'3,3'4,4'-Octahydro-3,3'-dimethyl-4,4'-biphenanthryl."Enantiomer. 5. 129-133 (2000)
[Publications] T.Nehira,N.Harada: "Circular Dichroism and Absolute Stereochemistry of [8] Paracyclophane-10-carbonitrile and Related Compounds."Enantiomer. 5. 139-144 (2000)
[Publications] S.Murai,N.Harada: "Synthesis,Circular Dichroism, and Absolute Stereochemistry of a Fecht Acid Analog and Related Compounds."Enantiomer. 5. 197-202 (2000)
[Publications] M.Kosaka,N.Harada: "Enantioresolution by the Chiral Phthalic Acid Method : Absolute Configurations of Substituted Benzylic Alcohols."Chirality. 12. 362-365 (2000)
[Publications] V.Petrov,N.Harada: "Step By Step Filter based program for calculations of highly informative derivative curves."Computor in Chemistry. 24. 561-569 (2000)
[Publications] N.Harada: "2-Methoxy-2-(1-naphthyl) propionic Acid, a Powerful Chiral Auxiliary for Enantioresolution of Alcohols and Determination of Their Absolute Configurations by the ^1H NMR Anisotropy Method."Tetrahedron : Asymmetry. 11. 1249-1253 (2000)
[Publications] N.Harada: "Molecular Chirality by Isotopic Substitution. Synthesis, Absolute Configuration, and CD Spectra of ^<13>C Substituted Chiral Diphenylmethanol."J.Phys.Org.Chem.. 13. 422-425 (2000)
[Publications] K.Monde,N.Harada: "Synthesis and Absolutestereochemistry of a Cruciferous Phytoalexin,(-)-Spirobrassinin."Chem.Lett.. 886-887 (2000)
[Publications] M.K.J.ter Wiel,N.Harada: "Chiral Overcrowded Alkenes ; Asymmetric Synthesis of (3S,3'S)-(M,M)-(E)-(+)-1,1'2,2'3,3'4,4'-Octahydro-3,3'7,7'-tetramethyl-4,4'-biphenanthrylidenes."Chirality. 12(in press). (2000)
[Publications] K.Monde,N.Harada: "Enantiomeric Excess of a Cruciferous Phytoalexin, Spirobrassinin and Its Enantiomeric Enrichment an Achiral HPLC System."J.Nat.Prod.. 63. 1312-1314 (2000)
[Publications] A.Ichikawa,N.Harada: "Absolute Configuration of 2-Methoxy-2-(2-naphthyl)propionic Acid, as Determined by the ^1H NMR Anisotropy Method."Tetrahedron : Asymmetry. 11. 2669-2675 (2000)
[Publications] N.Harada: "Chemistry of Unique Chiral Olefins-a Light-Powered Chiral Molecular Motor with Monodirectional Roration-(in Japanese)."J.Chem.Soc.Jpn.. 591-603 (2000)
[Publications] N.Morohashi,S.Miyano: "Stereocontrolled Oxidation of a Thiacalix[4]arene to the Sulfinyl Counterpart of a Defined S=O Configuration."Tetrahedron Lett.. 41. 2933-2937 (2000)
[Publications] N.Morohashi,S.Miyano: "Novel Molecular Chirality in the Calixarene Family : Formation of Chiral Disulfinyldithia-calix [4] arenes via Partial Oxidation of Two Adjacent Sulfides of Tetrathiacalix [4] arene."Tetrahedron Lett.. 41. 5093-5097 (2000)
[Publications] N.Morohashi,S.Miyano: "Synthesis and Structural Characterization of a Pd^<2+> Complex with p-tert-Butylsulfinylcalix [4] arene."Chem.Lett.. 66-67 (2001)
[Publications] H.Katagiri,S.Miyano: "Calix [4] arenes Comprised of Aniline Units."J.Am.Chem.Soc.. 123. 779-780 (2001)
[Publications] 原田宣之: "化学と工業"分子機械「光動力キラル分子モーター」-その化学と回転機構-""日本化学会. 4 (2000)
[Publications] N.Harada: "Circular Dichroism : Principles and Applications, Circular Dichroism of Twisted π-Electron Systems : Theoretical Determination of the Absolute Stereochemistry of Matural Products and Chiral Synthetic Organic Compounds'"John Wiley & Sons, Inc, New York. 27 (2000)
[Publications] 原田宣之(分担): "機器分析実験「旋光性円二色性」"東京化学同人(印刷中). (2000)

2000 Fiscal Year Annual Research Report

分子キラリティー認識の新規円二色性法の開発と応用

Principal Investigator

原田 宣之 東北大学, 反応化学研究所, 教授 (30006324)

Research Products

[Publications] S.Kuwahara,N.Harada: "Enantioresolution and Absolute Stereochemistry of o-Substituted Diphenylmethanols."Enantiomer. 5. 109-114 (2000)

[Publications] N.Koumura,N.Harada: "Synthesis, Circular Dichroism, and Absolute Stereochemistry of 1,1'2,2'3,3'4,4'-Octahydro-3,3'-dimethyl-4,4'-biphenanthryl."Enantiomer. 5. 129-133 (2000)

[Publications] T.Nehira,N.Harada: "Circular Dichroism and Absolute Stereochemistry of [8] Paracyclophane-10-carbonitrile and Related Compounds."Enantiomer. 5. 139-144 (2000)

[Publications] S.Murai,N.Harada: "Synthesis,Circular Dichroism, and Absolute Stereochemistry of a Fecht Acid Analog and Related Compounds."Enantiomer. 5. 197-202 (2000)

[Publications] M.Kosaka,N.Harada: "Enantioresolution by the Chiral Phthalic Acid Method : Absolute Configurations of Substituted Benzylic Alcohols."Chirality. 12. 362-365 (2000)

[Publications] V.Petrov,N.Harada: "Step By Step Filter based program for calculations of highly informative derivative curves."Computor in Chemistry. 24. 561-569 (2000)

[Publications] N.Harada: "2-Methoxy-2-(1-naphthyl) propionic Acid, a Powerful Chiral Auxiliary for Enantioresolution of Alcohols and Determination of Their Absolute Configurations by the ^1H NMR Anisotropy Method."Tetrahedron : Asymmetry. 11. 1249-1253 (2000)

[Publications] N.Harada: "Molecular Chirality by Isotopic Substitution. Synthesis, Absolute Configuration, and CD Spectra of ^<13>C Substituted Chiral Diphenylmethanol."J.Phys.Org.Chem.. 13. 422-425 (2000)

[Publications] K.Monde,N.Harada: "Synthesis and Absolutestereochemistry of a Cruciferous Phytoalexin,(-)-Spirobrassinin."Chem.Lett.. 886-887 (2000)

[Publications] M.K.J.ter Wiel,N.Harada: "Chiral Overcrowded Alkenes ; Asymmetric Synthesis of (3S,3'S)-(M,M)-(E)-(+)-1,1'2,2'3,3'4,4'-Octahydro-3,3'7,7'-tetramethyl-4,4'-biphenanthrylidenes."Chirality. 12(in press). (2000)

[Publications] K.Monde,N.Harada: "Enantiomeric Excess of a Cruciferous Phytoalexin, Spirobrassinin and Its Enantiomeric Enrichment an Achiral HPLC System."J.Nat.Prod.. 63. 1312-1314 (2000)

[Publications] A.Ichikawa,N.Harada: "Absolute Configuration of 2-Methoxy-2-(2-naphthyl)propionic Acid, as Determined by the ^1H NMR Anisotropy Method."Tetrahedron : Asymmetry. 11. 2669-2675 (2000)

[Publications] N.Harada: "Chemistry of Unique Chiral Olefins-a Light-Powered Chiral Molecular Motor with Monodirectional Roration-(in Japanese)."J.Chem.Soc.Jpn.. 591-603 (2000)

[Publications] N.Morohashi,S.Miyano: "Stereocontrolled Oxidation of a Thiacalix[4]arene to the Sulfinyl Counterpart of a Defined S=O Configuration."Tetrahedron Lett.. 41. 2933-2937 (2000)

[Publications] N.Morohashi,S.Miyano: "Novel Molecular Chirality in the Calixarene Family : Formation of Chiral Disulfinyldithia-calix [4] arenes via Partial Oxidation of Two Adjacent Sulfides of Tetrathiacalix [4] arene."Tetrahedron Lett.. 41. 5093-5097 (2000)

[Publications] N.Morohashi,S.Miyano: "Synthesis and Structural Characterization of a Pd^<2+> Complex with p-tert-Butylsulfinylcalix [4] arene."Chem.Lett.. 66-67 (2001)

[Publications] H.Katagiri,S.Miyano: "Calix [4] arenes Comprised of Aniline Units."J.Am.Chem.Soc.. 123. 779-780 (2001)

[Publications] 原田宣之: "化学と工業"分子機械「光動力キラル分子モーター」-その化学と回転機構-""日本化学会. 4 (2000)

[Publications] N.Harada: "Circular Dichroism : Principles and Applications, Circular Dichroism of Twisted π-Electron Systems : Theoretical Determination of the Absolute Stereochemistry of Matural Products and Chiral Synthetic Organic Compounds'"John Wiley & Sons, Inc, New York. 27 (2000)

[Publications] 原田宣之(分担): "機器分析実験「旋光性円二色性」"東京化学同人(印刷中). (2000)

原田宣之東北大学, 反応化学研究所, 教授 (30006324)